WO2014193039A1 - Thermoplastic resin composition having excellent conductivity and impact strength - Google Patents

Thermoplastic resin composition having excellent conductivity and impact strength Download PDF

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Publication number
WO2014193039A1
WO2014193039A1 PCT/KR2013/007805 KR2013007805W WO2014193039A1 WO 2014193039 A1 WO2014193039 A1 WO 2014193039A1 KR 2013007805 W KR2013007805 W KR 2013007805W WO 2014193039 A1 WO2014193039 A1 WO 2014193039A1
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WIPO (PCT)
Prior art keywords
aromatic vinyl
weight
thermoplastic resin
resin composition
rubber
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PCT/KR2013/007805
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French (fr)
Korean (ko)
Inventor
정은혜
신찬균
임종철
Original Assignee
제일모직주식회사
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Priority to JP2016516431A priority Critical patent/JP6076542B2/en
Publication of WO2014193039A1 publication Critical patent/WO2014193039A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a conductive thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition excellent in conductivity and impact strength.
  • Electrostatic coating is performed on the thermoplastic resin after the primer treatment for imparting conductivity.
  • Electrostatic painting is a method of adsorbing paint by applying charge to the paint in the sprayed state and applying a high voltage to the paint. Specifically, a positive electrode is applied to the coating material, and a negative electrode is applied to the spraying device, and the paint particles are adsorbed onto the coating material by applying (-) static electricity to the sprayed paint particles. Electrostatic coating is less paint loss than general spray method, the quality and performance of the coating film is excellent, automatic installation is possible, and coating is possible regardless of the size of the painting.
  • the surface of the coating must be coated with a carbon solution before electrostatic coating to apply a primer treatment.
  • additional equipment, space and cost for primer treatment are required, and the quality of the coating film varies according to the primer coating thickness, and if the primer treatment is not uniformly performed on the surface of the coating, electrostatic coating Coating efficiency is reduced.
  • the present inventors add carbon nanotubes to a thermoplastic resin to impart conductivity of the resin itself, thereby enabling electrostatic coating without a primer treatment, and specifying a composition ratio of the thermoplastic resin to add carbon nanotubes.
  • a thermoplastic resin composition that can prevent the deterioration of physical properties.
  • An object of the present invention is to provide a thermoplastic resin composition having excellent conductivity.
  • Another object of the present invention is to provide a thermoplastic resin composition excellent in impact strength.
  • Another object of the present invention is to provide a thermoplastic resin composition capable of electrostatic coating without primer treatment.
  • Still another object of the present invention is to provide a thermoplastic resin composition having excellent electrostatic coating efficiency.
  • the conductive thermoplastic resin composition according to the present invention is (A) 15 to 35% by weight of the rubber-modified aromatic vinyl graft copolymer of the core-shell structure having an average particle diameter of 2,000 to 5,000 kPa, (B) 500 to 1,500 kPa 5 to 15% by weight of a rubber-modified aromatic vinyl graft copolymer having a phosphorus core-shell structure, and (C) a base comprising 50 to 80% by weight of an aromatic vinyl copolymer having a weight average molecular weight of 70,000 to 120,000 g / mol. It may contain 1 to 5 parts by weight of (D) carbon nanotubes based on 100 parts by weight of the resin.
  • the carbon nanotubes (D) may have an average particle diameter of 5 to 100 nm and an average length of 1 to 50 ⁇ m.
  • the rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure having an average particle diameter of 2,000 to 5,000 mm 3 is contained in an aromatic vinyl monomer 34 to 5 to 65 wt% of a rubbery polymer having an average particle diameter of 50 to 500 mm 3. It can be prepared by graft polymerization of 94% by weight and 1 to 30% by weight of the copolymerizable monomer with the aromatic vinyl monomer.
  • the rubber-modified aromatic vinyl graft copolymer (B) having a core-shell structure having an average particle diameter of 500 to 1,500 mm 3 is contained in an aromatic vinyl monomer of 34 to 94 to 5 to 65 wt% of a rubbery polymer having an average particle diameter of 20 to 300 mm 3. It may be prepared by graft polymerization of 1% to 30% by weight and a monomer copolymerizable with the aromatic vinyl monomer.
  • the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure and the rubber-modified aromatic vinyl graft copolymer (B) of the core-shell structure include unsaturated carboxylic acid, unsaturated carboxylic anhydride, Maleimide-based monomers or mixtures thereof may be further graft polymerized to 0-15% by weight.
  • the aromatic vinyl copolymer (C) having a weight average molecular weight of 70,000 to 120,000 g / mol is obtained by polymerizing 60 to 90% by weight of an aromatic vinyl monomer and 10 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer.
  • the aromatic vinyl copolymer (C) may further polymerize 0 to 30% by weight of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, or a mixture thereof.
  • the rubbery polymer may be a diene rubber, a saturated rubber added with hydrogen to the diene rubber, an acrylate rubber, an ethylene-propylene-diene monomer terpolymer, a silicone rubber, or a mixture thereof.
  • the aromatic vinyl monomers are styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, or Mixtures thereof.
  • the monomer copolymerizable with the aromatic vinyl monomer may be an unsaturated nitrile monomer, an acrylic monomer, or a mixture thereof.
  • the conductive thermoplastic resin composition of the present invention may further include carbon black.
  • the conductive thermoplastic resin composition of the present invention may further include an impact modifier, an antidropping agent, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weather stabilizer, a pigment, a dye, a colorant, an inorganic additive, or a mixture thereof as an additive.
  • an impact modifier an antidropping agent, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weather stabilizer, a pigment, a dye, a colorant, an inorganic additive, or a mixture thereof as an additive.
  • the molded article according to the present invention is molded from the conductive thermoplastic resin composition according to the present invention.
  • the conductive thermoplastic resin composition according to the present invention has excellent conductivity and impact strength, can be electrostatically coated without a primer treatment, and has excellent efficiency of electrostatic coating.
  • the present invention relates to a conductive thermoplastic resin composition, and to a thermoplastic resin composition excellent in conductivity and impact strength.
  • the conductive thermoplastic resin composition according to the present invention is (A) 15 to 35% by weight of the rubber-modified aromatic vinyl graft copolymer of the core-shell structure having an average particle diameter of 2,000 to 5,000 kPa, (B) 500 to 1,500 kPa 5 to 15% by weight of a rubber-modified aromatic vinyl graft copolymer having a phosphorus core-shell structure, and (C) a base comprising 50 to 80% by weight of an aromatic vinyl copolymer having a weight average molecular weight of 70,000 to 120,000 g / mol. It may include 1 to 5 parts by weight of (D) carbon nanotubes based on 100 parts by weight of the resin.
  • thermoplastic resin composition a rubber-modified aromatic vinyl-based graft copolymer having a core-shell structure of a large particle diameter prepared by a method known to those skilled in the art or commercially available ( A) can be used without limitation.
  • the average particle diameter of the rubber-modified aromatic vinyl graft copolymer (A) having a large particle size core-shell structure may be 2,000 to 5,000 mm 3, and preferably 2,000 to 3,000 mm 3. When the average particle diameter is less than 2,000 mm 3, the impact strength of the thermoplastic resin composition may decrease.
  • the rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure having a large particle diameter is a graft copolymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubbery polymer having an average particle diameter of 50 to 500 mm 3.
  • the rubber-modified aromatic vinyl graft copolymer (A) having a large particle diameter core-shell structure is 5 to 65% by weight of a rubbery polymer having an average particle diameter of 50 to 500 mm 3, 34 to 94% by weight of an aromatic vinyl monomer and the aromatic vinyl 1 to 30% by weight of the monomer copolymerizable with the monomer is graft polymerized.
  • 0-15% by weight of further grafted unsaturated carboxylic acid, unsaturated carboxylic anhydride, maleimide monomer and mixtures thereof may be further graft polymerized to the rubbery polymer to provide heat resistance and processability.
  • the rubbery polymer may be a diene rubber, a saturated rubber added with hydrogen to the diene rubber, an acrylate rubber, an ethylene-propylene-diene monomer terpolymer, a silicone rubber, or a mixture thereof.
  • the diene rubber may be polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), polyisoprene, or mixtures thereof.
  • Acrylate rubbers include polymethyl acrylate, polyethyl acrylate, polyn-propyl acrylate, polyn-butyl acrylate, poly2-ethylhexyl acrylate, polyhexyl methacrylate, poly2-ethylhexyl methacryl Rate, or mixtures thereof.
  • Silicone rubbers include polyhexamethyl cyclotrisiloxane, polyoctamethyl cyclosiloxane, polydecamethyl cyclosiloxane, polydodecamethyl cyclosiloxane, polytrimethyltriphenyl cyclosiloxane, polytetramethyltetrapetyl cyclotetrosiloxane, polyoctaphenyl cyclo Tetrasiloxane, or mixtures thereof.
  • diene rubber may be preferably selected, and butadiene rubber may be more preferably selected.
  • the rubbery polymer may have an average particle diameter of 50 to 500 mm 3. When the average particle diameter of the rubbery polymer is included in the above range, the impact strength and appearance are excellent.
  • Aromatic vinyl monomers are styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, or Mixtures thereof.
  • the monomer copolymerizable with the aromatic vinyl monomer may be an unsaturated nitrile monomer, an acrylic monomer, or a mixture thereof.
  • the nitrile-based monomer may be acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof.
  • the acrylic monomers may be methyl acrylate, methyl methacrylate, or mixtures thereof.
  • the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle diameter is a unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, or a carboxylic acid in order to impart heat resistance and workability.
  • the mixture can be further graft polymerized from 0 to 15% by weight.
  • the unsaturated carboxylic acid may be acrylic acid or methacrylic acid.
  • Unsaturated carboxylic anhydride is maleic anhydride.
  • the maleimide monomer may be alkyl, or nuclear substituted maleimide.
  • the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle size is a rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle size, a core-shell having a small particle size.
  • the rubber-modified aromatic vinyl graft copolymer (B) and the aromatic vinyl copolymer (C) of the structure may include 15 to 35% by weight.
  • the content of the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle size is less than 15% by weight, the impact strength of the thermoplastic resin composition is lowered, and when the content is more than 35% by weight, carbon in the thermoplastic resin composition Dispersibility of the nanotubes may be reduced.
  • a core having a small particle size between the rubber-modified aromatic vinyl graft copolymer (A) having a large particle size core-shell structure may be located, and thus dispersibility of carbon nanotubes may be improved.
  • the average particle diameter of the rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure may be 500 to 1,500 mm 3, and preferably 1,000 to 1,500 mm 3.
  • the rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure is graft copolymerized with a rubber polymer having an average particle diameter of 20 to 300 mm 3 and a monomer copolymerizable with an aromatic vinyl monomer and an aromatic vinyl monomer.
  • a rubber polymer having an average particle diameter of 20 to 300 mm 3 and a monomer copolymerizable with an aromatic vinyl monomer and an aromatic vinyl monomer.
  • Rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure is 5 to 65% by weight of a rubbery polymer having an average particle diameter of 20 to 300 mm 3, 34 to 94% by weight of an aromatic vinyl monomer and aromatic vinyl 1 to 30% by weight of the monomer copolymerizable with the monomer is graft polymerized.
  • 0-15% by weight of further grafted unsaturated carboxylic acid, unsaturated carboxylic anhydride, maleimide monomer, or mixtures thereof may be further graft polymerized to the rubbery polymer to impart heat resistance and processability.
  • the monomer copolymerizable with the rubbery polymer, the aromatic vinylic monomer and the aromatic vinylic monomer includes the rubbery polymer, the aromatic vinylic monomer and the aromatic vinyl described in the rubber-modified aromatic vinyl-based graft copolymer (A) having the above-mentioned core-shell structure. It is the same as the monomer copolymerizable with the monomer and the description is omitted in order to avoid duplication.
  • the rubber-modified aromatic vinyl graft copolymer (B) having a core-shell structure of a small particle size is a rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure of a large particle size, and a core- of a small particle size. 5 to 15 wt% of the rubber-modified aromatic vinyl graft copolymer (B) and the aromatic vinyl copolymer (C) having a shell structure may be included.
  • the content of the rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure is less than 5% by weight, the dispersibility of carbon nanotubes may be lowered, thereby lowering the conductivity of the thermoplastic resin composition.
  • an aromatic vinyl copolymer (C) prepared by a method known to those skilled in the art or commercially available may be used without limitation.
  • the aromatic vinyl copolymer (C) include an alternating copolymer, a random copolymer, a block copolymer, and the like, and the copolymer does not include a graft copolymer.
  • the aromatic vinyl copolymer (C) may have a weight average molecular weight of 70,000 to 120,000 g / mol, preferably 90,000 to 110,000 g / mol. When the weight average molecular weight of the aromatic vinyl copolymer (C) is more than 120,000 g / mol, dispersibility of the carbon nanotubes may decrease.
  • the aromatic vinyl copolymer (C) may be prepared by copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer. It can also be prepared by further copolymerizing monomers which optionally provide processability and heat resistance.
  • the aromatic vinyl copolymer (C) may be prepared by polymerizing 60 to 90% by weight of an aromatic vinyl monomer and 10 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer.
  • the aromatic vinyl monomers are styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, or mixtures thereof Can be.
  • styrene can be used.
  • the monomer copolymerizable with the aromatic vinyl monomer may be an unsaturated nitrile monomer, an acrylic monomer, or a mixture thereof.
  • the unsaturated nitrile monomer may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or a mixture thereof.
  • the acrylic monomers may be methyl acrylate, methyl methacrylate, or mixtures thereof.
  • the aromatic vinyl copolymer (C) may further polymerize 0 to 30% by weight of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, or a mixture thereof in order to impart heat resistance and processability.
  • the unsaturated carboxylic acid may be acrylic acid or methacrylic acid.
  • the unsaturated carboxylic anhydride may be maleic anhydride.
  • the maleimide monomer may be alkyl, or nuclear substituted maleimide.
  • the aromatic vinyl copolymer (C) is a rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure of a large particle size, and a rubber-modified aromatic vinyl graft copolymer having a core-shell structure of a small particle size.
  • (B) 50 to 80% by weight based on 100% by weight of the aromatic vinyl copolymer (C).
  • the content of the aromatic vinyl copolymer (C) is more than 80% by weight, the impact strength of the thermoplastic resin composition may decrease.
  • thermoplastic resin composition according to the present invention may be prepared by a method known to those skilled in the art, or commercially available carbon nanotubes (D) may be used without limitation. Since carbon nanotubes (D) lower the surface resistance of the thermoplastic resin composition and increase the conductivity of the thermoplastic resin composition, the carbon nanotube (D) enables electrostatic coating even without a primer treatment.
  • the method of synthesizing carbon nanotubes is arc-discharge, pyrolysis, laser vaporization, plasma chemical vapor deposition, and thermal chemical vapor deposition. , Electrolysis, flame synthesis, and the like, but the carbon nanotubes (D) used in the present invention may use all of the obtained carbon nanotubes regardless of the synthesis method.
  • Carbon nanotubes can be divided into single wall carbon nanotubes, double wall carbon nanotubes, multi wall carbon nanotubes, and truncated cones depending on the number of walls. It can be divided into a cup-stacked carbon nanofiber having a hollow tube shape in which a plurality of truncated graphenes are stacked. Carbon nanotubes (D) used in the present invention is not limited to the kind, it is economically preferable to use multi-walled carbon nanotubes.
  • the carbon nanotubes (D) may have an average particle diameter of 5 to 100 nm, an average length of 1 to 50 ⁇ m, preferably an average particle diameter of 5 to 30 nm, and an average length of 1 to 50 ⁇ m.
  • the carbon nanotube (D) is a rubber-modified aromatic vinyl graft copolymer (A) of a core-shell structure of a large particle size, a rubber-modified aromatic vinyl graft copolymer (B) of a core-shell structure of a small particle size (B) ), 1 to 5 parts by weight based on 100 parts by weight of the aromatic vinyl copolymer (C).
  • the content of the carbon nanotubes (D) is less than 1 part by weight, the conductivity of the thermoplastic resin composition is lowered, and when it is more than 5 parts by weight, the impact strength of the thermoplastic resin composition may be lowered.
  • carbon black may be further used as a conductive agent.
  • the carbon black has a specific surface area of 50 to 1500 m 2 / g and an average particle size of 10 to 100 nm in order to implement excellent electrical conductivity.
  • the carbon black may be ketjen black, acetylene balck, furnace black, channel black, timcal carbon black, or mixtures thereof. It is preferable to use Ketjen Black which is excellent in electrical conductivity among these.
  • Carbon black has excellent electrical conductivity, but has a property that carbon particles are likely to fall off due to scratches or friction, and thus, a large amount of wear occurs.
  • an excessive amount of carbon black is used, there is a problem that the extrudability of the molded article is reduced.
  • a fine conductive three-dimensional network structure can be formed between the carbon fibrils of the carbon nanotubes, thereby achieving stabilization of the surface resistance value and stabilization of carbon particle dropping.
  • the conductive agent (E) is a rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure of a large particle size, and a rubber-modified aromatic vinyl graft copolymer (B) having a core-shell structure of a small particle size.
  • aromatic vinyl copolymer (C) Based on 100 parts by weight of the aromatic vinyl copolymer (C), 0.5 to 10 parts by weight may be included.
  • the content of the conductive agent (E) is less than 0.5 parts by weight, the electrical conductivity is lowered, and when it is more than 10 parts by weight, mechanical properties and extrudability may be lowered.
  • thermoplastic resin composition of the present invention may further include an additive (F) according to each use of the resin composition.
  • the thermoplastic resin composition may further include an impact modifier, an antidropping agent, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weather stabilizer, a pigment, a dye, a colorant, an inorganic additive, or a mixture thereof.
  • the additive (F) is a rubber-modified aromatic vinyl graft copolymer (A) of a core-shell structure of a large particle size, a rubber-modified aromatic vinyl graft copolymer (B) of a core-shell structure of a small particle size, 10 parts by weight or less, preferably 0.0001 parts by weight to 10 parts by weight or less based on 100 parts by weight of the aromatic vinyl copolymer (C).
  • thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition.
  • the thermoplastic resin composition according to the present invention may be prepared in the form of pellets by a method of simultaneously mixing the components of the present invention and other additives and then melt extrusion in an extruder.
  • thermoplastic resin composition there is no particular limitation on the method for producing a molded article by molding the thermoplastic resin composition according to the present invention.
  • an extrusion, injection or cast molding method may be applied. Molding method can be easily carried out by those skilled in the art.
  • the molded article of the present invention has an Izod impact strength of 15 to 40 kgf ⁇ cm / cm for a molded article of 1/8 ′′ thickness measured at 23 ° C. in accordance with ASTM D256.
  • the molded article of the present invention has a surface resistance of 10 ⁇ 1 to 10 11 ⁇ s / ⁇ measured using Wolfgang Warmbler's SRM-100 according to ASTM D257.
  • the molded article of the present invention has a volume resistivity ( ⁇ ⁇ cm) of 10 ⁇ 1 to 10 8 ⁇ ⁇ cm measured using MY40 manufactured by YOKOGAWA Co., Ltd. in accordance with ASTM D257.
  • Cheil Industries AB03-CHA was used as g-ABS with an average particle diameter of 2,570 mm3.
  • Cheil Industries AB03-CHT was used as g-ABS with an average particle diameter of 1,300 mm 3.
  • Cheil Industries' CA03-AP-70 was used as a SAN having a weight average molecular weight of 95,000 g / mol.
  • VGCF-X As a carbon nanotube having an average particle diameter of 5 to 30 nm and an average length of 1 to 50 ⁇ m, VGCF-X, a multi-walled carbon nanotube manufactured by ShowaDenko, was used.
  • the mixing ratios of (A), (B) and (C) are represented by weight percent with respect to 100% by weight of (A), (B) and (C), and (D) is (A), (B) ) And (C) it is shown as a middle part with respect to 100 weight part of total.
  • Izod impact strength (kgfcm / cm): measured in 1/8 "thickness at 23 °C according to ASTM D 256.
  • volume resistivity ( ⁇ cm) It measured using MY40 by YOKOGAWA company based on ASTMD257.
  • the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure of the large particle size and the rubber-modified aromatic vinyl graft air of the core-shell structure of the small particle diameter included in the scope of the present invention In Example 1 using the copolymer (B), the aromatic vinyl copolymer (C) and the carbon nanotubes (D), the surface resistance was reduced according to the use of the carbon nanotubes (D), thereby improving the conductivity.
  • a rubber-modified aromatic vinyl graft copolymer (A) having a large particle size core-shell structure and a rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure are used together and have a specific range of weight.
  • An aromatic vinyl copolymer (C) having an average molecular weight was used to prevent a decrease in impact strength due to the use of carbon nanotubes (D).
  • Comparative Example 1 without using carbon nanotubes (D) was too high surface resistance could not be measured
  • Comparative Example 2 using an aromatic vinyl copolymer (C) having a large weight average molecular weight is conductive and Both impact strengths were reduced.
  • Comparative Example 3 using a rubber-modified aromatic vinyl-based graft copolymer (B) having a small particle size core-shell structure, and a rubber-modified aromatic vinyl-based graphene having a core-shell structure having a small particle size, out of the content range of the present invention.
  • Comparative Example 4 without using the copolymer (B) the impact strength was lowered.
  • Comparative Example 5 used out of the range of the weight average molecular weight of the aromatic vinyl copolymer (C) both the conductivity and the impact strength were reduced.
  • Example 1 included in the scope of the present invention was superior in volume resistance and coating efficiency compared to Comparative Examples 1 and 2 not included in the scope of the present invention.

Abstract

A conductive thermoplastic resin composition, according to the present invention, comprises: 100 parts by weight of a base resin including (A) 15 to 35 wt% of a rubber-modified aromatic vinyl-based graft copolymer having an average diameter of 2,000-5,000 Å and a core-shell structure, B) 5 to 15 wt% of a rubber-modified aromatic vinyl-based graft copolymer having an average diameter of 500-1,500 Å and a core-shell structure, and C) 50 to 80 wt% of an aromatic vinyl-based graft copolymer having a weight-average molecular weight of 70,000-120,000 g/mol; and D) 1 to 5 parts by weight of carbon nanotubes on the basis of the 100 parts by weight of the base resin. The conductive thermoplastic resin composition, according to the present invention, maintains excellent impact strength and enhances surface resistance through the dispersion of carbon nanotubes, and thus can be used for electrostatic painting without need for a primer treatment

Description

전도성 및 충격강도가 우수한 열가소성 수지 조성물Thermoplastic resin composition with excellent conductivity and impact strength
본 발명은 전도성 열가소성 수지 조성물에 관한 것이다. 보다 구체적으로, 본 발명은 전도성 및 충격강도가 우수한 열가소성 수지 조성물에 관한 것이다.The present invention relates to a conductive thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition excellent in conductivity and impact strength.
열가소성 수지는 물품에 도장하는 경우에, 전도성을 부여하기 위하여 프라이머 처리를 한 후 열가소성 수지로 정전도장을 하고 있다. 정전도장(electrostatic painting)이란 분무상태의 도료에 전하를 부여하고, 도장물에 고전압을 가함으로써 도료를 흡착도장하는 방법이다. 구체적으로 도장물에는 양극을, 분무장치에는 음극을 걸어, 분사되는 도료입자에 (-) 정전기를 띠게 하여 도료입자를 도장물에 흡착시킨다. 정전도장은 일반적인 스프레이 방법에 비하여 도료손실이 적고, 도장막의 품질이나 성능이 우수하고, 자동설비가 가능하며, 도장물의 크기에 관계없이 도장이 가능하다.When the thermoplastic resin is coated on an article, electrostatic coating is performed on the thermoplastic resin after the primer treatment for imparting conductivity. Electrostatic painting is a method of adsorbing paint by applying charge to the paint in the sprayed state and applying a high voltage to the paint. Specifically, a positive electrode is applied to the coating material, and a negative electrode is applied to the spraying device, and the paint particles are adsorbed onto the coating material by applying (-) static electricity to the sprayed paint particles. Electrostatic coating is less paint loss than general spray method, the quality and performance of the coating film is excellent, automatic installation is possible, and coating is possible regardless of the size of the painting.
그러나, 정전도장을 하기 위해서는 정전도장 전에 도장물 표면을 탄소용액으로 코팅하여 전도성을 가하는 프라이머 처리를 해야만 한다. 이러한 프라이머 처리를 하는 경우, 프라이머 처리를 하기 위한 장치, 공간 및 비용이 추가적으로 필요하고, 프라이머 코팅 두께에 따라 도장막의 품질이 달라지며, 도장물의 표면에 프라이머 처리가 균일하게 이루어지지 않는 경우, 정전도장에 의한 도장효율이 저하된다.However, in order to perform electrostatic coating, the surface of the coating must be coated with a carbon solution before electrostatic coating to apply a primer treatment. In the case of such primer treatment, additional equipment, space and cost for primer treatment are required, and the quality of the coating film varies according to the primer coating thickness, and if the primer treatment is not uniformly performed on the surface of the coating, electrostatic coating Coating efficiency is reduced.
이에 본 발명자들은 상기와 같은 문제점을 해결하고자, 열가소성 수지에 탄소나노튜브를 첨가하여 수지 자체의 전도성을 부여함으로써 프라이머 처리 없이도 정전도장을 가능하게 하고, 열가소성 수지의 조성비를 특정하여 탄소나노튜브 첨가에 따른 물성저하를 방지할 수 있는 전도성 열가소성 수지 조성물을 개발하기에 이른 것이다.In order to solve the above problems, the present inventors add carbon nanotubes to a thermoplastic resin to impart conductivity of the resin itself, thereby enabling electrostatic coating without a primer treatment, and specifying a composition ratio of the thermoplastic resin to add carbon nanotubes. To develop a conductive thermoplastic resin composition that can prevent the deterioration of physical properties.
본 발명의 목적은 전도성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition having excellent conductivity.
본 발명의 다른 목적은 충격강도가 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition excellent in impact strength.
본 발명의 또 다른 목적은 프라이머 처리없이 정전도장이 가능한 열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition capable of electrostatic coating without primer treatment.
본 발명의 또 다른 목적은 정전도장 효율이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다. Still another object of the present invention is to provide a thermoplastic resin composition having excellent electrostatic coating efficiency.
본 발명의 상기 및 기타의 목적들은 모두 하기 설명되는 본 발명에 의해서 달성될 수 있다.Both the above and other objects of the present invention can be achieved by the present invention described below.
본 발명에 따른 전도성 열가소성 수지 조성물은 (A) 평균입경이 2,000 내지 5,000 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체 15 내지 35 중량%, (B) 평균입경이 500 내지 1,500 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체 5 내지 15 중량%, 및 (C) 중량평균분자량이 70,000 내지 120,000 g/mol인 방향족 비닐계 공중합체 50 내지 80 중량%를 포함하는 기초수지 100 중량부에 대하여, (D) 탄소나노튜브 1 내지 5 중량부 포함할 수 있다. The conductive thermoplastic resin composition according to the present invention is (A) 15 to 35% by weight of the rubber-modified aromatic vinyl graft copolymer of the core-shell structure having an average particle diameter of 2,000 to 5,000 kPa, (B) 500 to 1,500 kPa 5 to 15% by weight of a rubber-modified aromatic vinyl graft copolymer having a phosphorus core-shell structure, and (C) a base comprising 50 to 80% by weight of an aromatic vinyl copolymer having a weight average molecular weight of 70,000 to 120,000 g / mol. It may contain 1 to 5 parts by weight of (D) carbon nanotubes based on 100 parts by weight of the resin.
상기 탄소나노튜브(D)는 평균입경이 5 내지 100 nm이고, 평균길이가 1 내지 50 ㎛일 수 있다.The carbon nanotubes (D) may have an average particle diameter of 5 to 100 nm and an average length of 1 to 50 μm.
상기 평균입경이 2,000 내지 5,000 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)는 평균입경이 50 내지 500 Å인 고무질 중합체 5 내지 65 중량%에, 방향족 비닐계 단량체 34 내지 94 중량% 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체 1 내지 30 중량%를 그라프트 중합시켜 제조될 수 있다.The rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure having an average particle diameter of 2,000 to 5,000 mm 3 is contained in an aromatic vinyl monomer 34 to 5 to 65 wt% of a rubbery polymer having an average particle diameter of 50 to 500 mm 3. It can be prepared by graft polymerization of 94% by weight and 1 to 30% by weight of the copolymerizable monomer with the aromatic vinyl monomer.
평균입경이 500 내지 1,500 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)는 평균입경이 20 내지 300 Å인 고무질 중합체 5 내지 65 중량%에, 방향족 비닐계 단량체 34 내지 94 중량% 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체 1 내지 30 중량% 그라프트 중합시켜 제조될 수 있다.The rubber-modified aromatic vinyl graft copolymer (B) having a core-shell structure having an average particle diameter of 500 to 1,500 mm 3 is contained in an aromatic vinyl monomer of 34 to 94 to 5 to 65 wt% of a rubbery polymer having an average particle diameter of 20 to 300 mm 3. It may be prepared by graft polymerization of 1% to 30% by weight and a monomer copolymerizable with the aromatic vinyl monomer.
코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A) 및 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)는 고무질 중합체에 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체 또는 이들의 혼합물이 0 내지 15 중량%로 더 그라프트 중합될 수 있다.The rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure and the rubber-modified aromatic vinyl graft copolymer (B) of the core-shell structure include unsaturated carboxylic acid, unsaturated carboxylic anhydride, Maleimide-based monomers or mixtures thereof may be further graft polymerized to 0-15% by weight.
중량평균분자량이 70,000 내지 120,000 g/mol인 방향족 비닐계 공중합체(C)는 방향족 비닐계 단량체 60 내지 90 중량% 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체 10 내지 40 중량%를 중합시킨 것이다.The aromatic vinyl copolymer (C) having a weight average molecular weight of 70,000 to 120,000 g / mol is obtained by polymerizing 60 to 90% by weight of an aromatic vinyl monomer and 10 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer.
방향족 비닐계 공중합체(C)는 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체, 또는 이들의 혼합물이 0 내지 30 중량% 더 중합될 수 있다.The aromatic vinyl copolymer (C) may further polymerize 0 to 30% by weight of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, or a mixture thereof.
고무질 중합체는 디엔계 고무, 디엔계 고무에 수소를 첨가한 포화고무, 아크릴레이트계 고무, 에틸렌-프로필렌-디엔 단량체 삼원공중합체, 실리콘계 고무, 또는 이들의 혼합물일 수 있다.The rubbery polymer may be a diene rubber, a saturated rubber added with hydrogen to the diene rubber, an acrylate rubber, an ethylene-propylene-diene monomer terpolymer, a silicone rubber, or a mixture thereof.
방향족 비닐계 단량체는 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, 파라 t-부틸스티렌, 에틸스티렌, 비닐 크실렌, 모노클로로스티렌, 디클로로스티렌, 디브로모스티렌, 비닐 나프탈렌, 또는 이들의 혼합물일 수 있다.The aromatic vinyl monomers are styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, or Mixtures thereof.
방향족 비닐계 단량체와 공중합이 가능한 단량체는 불포화 니트릴계 단량체, 아크릴계 단량체, 또는 이들의 혼합물일 수 있다.The monomer copolymerizable with the aromatic vinyl monomer may be an unsaturated nitrile monomer, an acrylic monomer, or a mixture thereof.
본 발명의 전도성 열가소성 수지 조성물은 카본블랙을 더 포함할 수 있다.The conductive thermoplastic resin composition of the present invention may further include carbon black.
본 발명의 전도성 열가소성 수지 조성물은 충격보강재, 적하 방지제, 산화 방지제, 가소제, 열안정제, 광안정제, 상용화제, 내후안정제, 안료, 염료, 착색제, 무기물 첨가제, 또는 이들의 혼합물을 첨가제로 더 포함할 수 있다.The conductive thermoplastic resin composition of the present invention may further include an impact modifier, an antidropping agent, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weather stabilizer, a pigment, a dye, a colorant, an inorganic additive, or a mixture thereof as an additive. Can be.
본 발명에 따른 성형품은 상기 본 발명에 따른 전도성 열가소성 수지 조성물로부터 성형된다.The molded article according to the present invention is molded from the conductive thermoplastic resin composition according to the present invention.
이하 본 발명의 구체적인 내용을 하기에 상세히 설명한다.Hereinafter, specific contents of the present invention will be described in detail below.
본 발명에 따른 전도성 열가소성 수지 조성물은 전도성 및 충격강도가 우수하고, 프라이머 처리없이 정전도장 가능하며, 정전도장의 효율이 우수하다.The conductive thermoplastic resin composition according to the present invention has excellent conductivity and impact strength, can be electrostatically coated without a primer treatment, and has excellent efficiency of electrostatic coating.
본 발명은 전도성 열가소성 수지 조성물에 관한 것으로, 전도성 및 충격강도가 우수한 열가소성 수지 조성물에 관한 것이다.The present invention relates to a conductive thermoplastic resin composition, and to a thermoplastic resin composition excellent in conductivity and impact strength.
본 발명에 따른 전도성 열가소성 수지 조성물은 (A) 평균입경이 2,000 내지 5,000 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체 15 내지 35 중량%, (B) 평균입경이 500 내지 1,500 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체 5 내지 15 중량%, 및 (C) 중량평균분자량이 70,000 내지 120,000 g/mol인 방향족 비닐계 공중합체 50 내지 80 중량%를 포함하는 기초수지 100 중량부에 대하여, (D) 탄소나노튜브 1 내지 5 중량부를 포함할 수 있다.The conductive thermoplastic resin composition according to the present invention is (A) 15 to 35% by weight of the rubber-modified aromatic vinyl graft copolymer of the core-shell structure having an average particle diameter of 2,000 to 5,000 kPa, (B) 500 to 1,500 kPa 5 to 15% by weight of a rubber-modified aromatic vinyl graft copolymer having a phosphorus core-shell structure, and (C) a base comprising 50 to 80% by weight of an aromatic vinyl copolymer having a weight average molecular weight of 70,000 to 120,000 g / mol. It may include 1 to 5 parts by weight of (D) carbon nanotubes based on 100 parts by weight of the resin.
(A) 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A) Rubber-modified aromatic vinyl graft copolymer of core-shell structure of large particle size
본 발명에 따른 열가소성 수지 조성물에는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 알려진 방법에 의해 제조되거나, 상업적으로 구입 가능한 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)가 제한 없이 사용될 수 있다. In the thermoplastic resin composition according to the present invention, a rubber-modified aromatic vinyl-based graft copolymer having a core-shell structure of a large particle diameter prepared by a method known to those skilled in the art or commercially available ( A) can be used without limitation.
대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)의 평균입경은 2,000 내지 5,000 Å이고, 바람직하게는 2,000 내지 3,000 Å일 수 있다. 평균입경이 2,000 Å 미만인 경우, 열가소성 수지 조성물의 충격강도가 저하될 수 있다.The average particle diameter of the rubber-modified aromatic vinyl graft copolymer (A) having a large particle size core-shell structure may be 2,000 to 5,000 mm 3, and preferably 2,000 to 3,000 mm 3. When the average particle diameter is less than 2,000 mm 3, the impact strength of the thermoplastic resin composition may decrease.
대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)는 평균입경이 50 내지 500 Å인 고무질 중합체에, 방향족 비닐계 단량체 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체를 그라프트 공중합시켜 제조할 수 있다. 또한, 선택적으로 가공성 및 내열성을 부여하는 단량체를 그라프트 공중합시켜 제조할 수 있다.The rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure having a large particle diameter is a graft copolymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubbery polymer having an average particle diameter of 50 to 500 mm 3. Can be prepared. It can also be prepared by graft copolymerization of monomers that selectively impart processability and heat resistance.
대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)는 평균입경이 50 내지 500 Å인 고무질 중합체 5 내지 65 중량%에, 방향족 비닐계 단량체 34 내지 94 중량% 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체 1 내지 30 중량%를 그라프트 중합시킨 것이다. 또한, 선택적으로 내열성 및 가공성을 부여하기 위하여 상기 고무질 중합체에 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체 및 이들의 혼합물을 0 내지 15 중량% 더 그라프트 중합시킬 수 있다. The rubber-modified aromatic vinyl graft copolymer (A) having a large particle diameter core-shell structure is 5 to 65% by weight of a rubbery polymer having an average particle diameter of 50 to 500 mm 3, 34 to 94% by weight of an aromatic vinyl monomer and the aromatic vinyl 1 to 30% by weight of the monomer copolymerizable with the monomer is graft polymerized. In addition, 0-15% by weight of further grafted unsaturated carboxylic acid, unsaturated carboxylic anhydride, maleimide monomer and mixtures thereof may be further graft polymerized to the rubbery polymer to provide heat resistance and processability.
고무질 중합체는 디엔계 고무, 디엔계 고무에 수소를 첨가한 포화고무, 아크릴레이트계 고무, 에틸렌-프로필렌-디엔 단량체 삼원공중합체, 실리콘계 고무, 또는 이들의 혼합물일 수 있다.The rubbery polymer may be a diene rubber, a saturated rubber added with hydrogen to the diene rubber, an acrylate rubber, an ethylene-propylene-diene monomer terpolymer, a silicone rubber, or a mixture thereof.
디엔계 고무는 폴리부타디엔, 폴리(스티렌-부타디엔), 폴리(아크릴로니트릴-부타디엔), 폴리이소프렌, 또는 이들의 혼합물일 수 있다. The diene rubber may be polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), polyisoprene, or mixtures thereof.
아크릴레이트계 고무는 폴리메틸 아크릴레이트, 폴리에틸 아크릴레이트, 폴리n-프로필 아크릴레이트, 폴리n-부틸 아크릴레이트, 폴리2-에틸헥실 아크릴레이트, 폴리헥실 메타크릴레이트, 폴리2-에틸헥실 메타크릴레이트, 또는 이들의 혼합물일 수 있다. Acrylate rubbers include polymethyl acrylate, polyethyl acrylate, polyn-propyl acrylate, polyn-butyl acrylate, poly2-ethylhexyl acrylate, polyhexyl methacrylate, poly2-ethylhexyl methacryl Rate, or mixtures thereof.
실리콘계 고무는 폴리헥사메틸 사이클로트리실록산, 폴리옥타메틸 사이클로실록산, 폴리데카메틸 사이클로실록산, 폴리도데카메틸 사이클로실록산, 폴리트리메틸트리페닐 사이클로실록산, 폴리테트라메틸테트라페틸 사이클로테트로실록산, 폴리옥타페닐 사이클로테트라실록산, 또는 이들의 혼합물일 수 있다. Silicone rubbers include polyhexamethyl cyclotrisiloxane, polyoctamethyl cyclosiloxane, polydecamethyl cyclosiloxane, polydodecamethyl cyclosiloxane, polytrimethyltriphenyl cyclosiloxane, polytetramethyltetrapetyl cyclotetrosiloxane, polyoctaphenyl cyclo Tetrasiloxane, or mixtures thereof.
고무질 중합체로서 바람직하게 디엔계 고무를 선택할 수 있으며, 더 바람직하게 부타디엔계 고무를 선택할 수 있다.As the rubbery polymer, diene rubber may be preferably selected, and butadiene rubber may be more preferably selected.
고무질 중합체는 평균입경이 50 내지 500 Å일 수 있다. 고무질 중합체의 평균입경이 상기 범위 내에 포함될 경우, 충격강도 및 외관이 우수하다.The rubbery polymer may have an average particle diameter of 50 to 500 mm 3. When the average particle diameter of the rubbery polymer is included in the above range, the impact strength and appearance are excellent.
방향족 비닐계 단량체는 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, 파라 t-부틸스티렌, 에틸 스티렌, 비닐 크실렌, 모노클로로스티렌, 디클로로스티렌, 디브로모스티렌, 비닐 나프탈렌, 또는 이들의 혼합물일 수 있다.Aromatic vinyl monomers are styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, or Mixtures thereof.
방향족 비닐계 단량체와 공중합이 가능한 단량체는 불포화 니트릴계 단량체, 아크릴계 단량체, 또는 이들의 혼합물일 수 있다.The monomer copolymerizable with the aromatic vinyl monomer may be an unsaturated nitrile monomer, an acrylic monomer, or a mixture thereof.
니트릴계 단량체는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 또는 이들의 혼합물일 수 있다. 아크릴계 단량체는 메틸 아크릴레이트, 메틸 메타크릴레이트, 또는 이들의 혼합물일 수 있다.The nitrile-based monomer may be acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. The acrylic monomers may be methyl acrylate, methyl methacrylate, or mixtures thereof.
대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)는 내열성 및 가공성을 부여하기 위하여, 고무질 중합체에 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체, 또는 이들의 혼합물을 0 내지 15 중량% 더 그라프트 중합시킬 수 있다.The rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle diameter is a unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, or a carboxylic acid in order to impart heat resistance and workability. The mixture can be further graft polymerized from 0 to 15% by weight.
불포화 카르복실산은 아크릴산 또는 메타크릴산일 수 있다. 불포화 카르복실산 무수물은 무수말레인산이다. 말레이미드계 단량체는 알킬, 또는 핵치환 말레이미드일 수 있다.The unsaturated carboxylic acid may be acrylic acid or methacrylic acid. Unsaturated carboxylic anhydride is maleic anhydride. The maleimide monomer may be alkyl, or nuclear substituted maleimide.
본 발명에서, 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)는 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A), 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B), 방향족 비닐계 공중합체(C) 100 중량%에 대하여, 15 내지 35 중량% 포함할 수 있다.In the present invention, the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle size is a rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle size, a core-shell having a small particle size. The rubber-modified aromatic vinyl graft copolymer (B) and the aromatic vinyl copolymer (C) of the structure may include 15 to 35% by weight.
대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)의 함량이 15 중량% 미만인 경우, 열가소성 수지 조성물의 충격강도가 저하되고, 35 중량% 초과인 경우, 열가소성 수지 조성물 내 탄소나노튜브의 분산성이 저하될 수 있다. When the content of the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure having a large particle size is less than 15% by weight, the impact strength of the thermoplastic resin composition is lowered, and when the content is more than 35% by weight, carbon in the thermoplastic resin composition Dispersibility of the nanotubes may be reduced.
(B) 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B) Rubber-modified aromatic vinyl graft copolymer of core-shell structure of small particle size
대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)만을 사용하는 경우, 탄소나노튜브의 분산성이 저하되므로, 탄소나노튜브의 분산성을 향상시키기 위하여 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)를 함께 사용한다. 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)를 사용하는 경우, 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A) 사이에 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)가 위치할 수 있어, 탄소나노튜브의 분산성이 향상될 수 있다.In the case where only the rubber-modified aromatic vinyl graft copolymer (A) having a large particle diameter core-shell structure is used, the dispersibility of carbon nanotubes decreases, so that the core-shell of small particle diameter is improved to improve the dispersibility of carbon nanotubes. A rubber modified aromatic vinyl graft copolymer (B) having a structure is used together. In the case of using a rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure, a core having a small particle size between the rubber-modified aromatic vinyl graft copolymer (A) having a large particle size core-shell structure The rubber-modified aromatic vinyl graft copolymer (B) having a shell structure may be located, and thus dispersibility of carbon nanotubes may be improved.
소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)의 평균입경은 500 내지 1,500 Å이고, 바람직하게는 1,000 내지 1,500 Å일 수 있다.The average particle diameter of the rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure may be 500 to 1,500 mm 3, and preferably 1,000 to 1,500 mm 3.
소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)는 평균입경이 20 내지 300 Å인 고무질 중합체에, 방향족 비닐계 단량체 및 방향족 비닐계 단량체와 공중합 가능한 단량체를 그라프트 공중합시켜 제조할 수 있다. 또한, 선택적으로 가공성 및 내열성을 부여하는 단량체를 그라프트 공중합시켜 제조할 수 있다.The rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure is graft copolymerized with a rubber polymer having an average particle diameter of 20 to 300 mm 3 and a monomer copolymerizable with an aromatic vinyl monomer and an aromatic vinyl monomer. Can be prepared. It can also be prepared by graft copolymerization of monomers that selectively impart processability and heat resistance.
소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)는 평균입경이 20 내지 300 Å인 고무질 중합체 5 내지 65 중량%에, 방향족 비닐계 단량체 34 내지 94 중량% 및 방향족 비닐계 단량체와 공중합 가능한 단량체 1 내지 30 중량%를 그라프트 중합시킨 것이다. 또한, 선택적으로 내열성 및 가공성을 부여하기 위하여 상기 고무질 중합체에 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체, 또는 이들의 혼합물을 0 내지 15 중량% 더 그라프트 중합시킬 수 있다.Rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure is 5 to 65% by weight of a rubbery polymer having an average particle diameter of 20 to 300 mm 3, 34 to 94% by weight of an aromatic vinyl monomer and aromatic vinyl 1 to 30% by weight of the monomer copolymerizable with the monomer is graft polymerized. In addition, 0-15% by weight of further grafted unsaturated carboxylic acid, unsaturated carboxylic anhydride, maleimide monomer, or mixtures thereof may be further graft polymerized to the rubbery polymer to impart heat resistance and processability.
고무질 중합체, 방향족 비닐계 단량체 및 방향족 비닐계 단량체와 공중합 가능한 단량체는 상기 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)에서 기재한 고무질 중합체, 방향족 비닐계 단량체 및 방향족 비닐계 단량체와 공중합 가능한 단량체와 동일하며, 중복을 피하기 위하여 기재를 생략한다.The monomer copolymerizable with the rubbery polymer, the aromatic vinylic monomer and the aromatic vinylic monomer includes the rubbery polymer, the aromatic vinylic monomer and the aromatic vinyl described in the rubber-modified aromatic vinyl-based graft copolymer (A) having the above-mentioned core-shell structure. It is the same as the monomer copolymerizable with the monomer and the description is omitted in order to avoid duplication.
본 발명에서, 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)는 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A), 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B), 방향족 비닐계 공중합체(C) 100 중량%에 대하여, 5 내지 15 중량% 포함될 수 있다. 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)의 함량이 5 중량% 미만인 경우, 탄소나노튜브의 분산성이 저하되어 열가소성 수지 조성물의 전도성이 저하될 수 있다.In the present invention, the rubber-modified aromatic vinyl graft copolymer (B) having a core-shell structure of a small particle size is a rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure of a large particle size, and a core- of a small particle size. 5 to 15 wt% of the rubber-modified aromatic vinyl graft copolymer (B) and the aromatic vinyl copolymer (C) having a shell structure may be included. When the content of the rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure is less than 5% by weight, the dispersibility of carbon nanotubes may be lowered, thereby lowering the conductivity of the thermoplastic resin composition.
(C) 방향족 비닐계 공중합체(C) aromatic vinyl copolymer
본 발명에 따른 열가소성 수지 조성물에는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 알려진 방법에 의해 제조되거나, 상업적으로 구입 가능한 방향족 비닐계 공중합체(C)가 제한 없이 사용될 수 있다. 방향족 비닐계 공중합체(C)의 예로는 교호 공중합체, 랜덤 공중합체, 블록 공중합체 등이 있으며, 상기 공중합체는 그라프트 공중합체를 포함하지 않는다.In the thermoplastic resin composition according to the present invention, an aromatic vinyl copolymer (C) prepared by a method known to those skilled in the art or commercially available may be used without limitation. Examples of the aromatic vinyl copolymer (C) include an alternating copolymer, a random copolymer, a block copolymer, and the like, and the copolymer does not include a graft copolymer.
방향족 비닐계 공중합체(C)는 중량평균분자량이 70,000 내지 120,000 g/mol이고, 바람직하게는 90,000 내지 110,000 g/mol일 수 있다. 방향족 비닐계 공중합체(C)의 중량평균분자량이 120,000 g/mol 초과인 경우, 탄소나노튜브의 분산성이 저하될 수 있다.The aromatic vinyl copolymer (C) may have a weight average molecular weight of 70,000 to 120,000 g / mol, preferably 90,000 to 110,000 g / mol. When the weight average molecular weight of the aromatic vinyl copolymer (C) is more than 120,000 g / mol, dispersibility of the carbon nanotubes may decrease.
방향족 비닐계 공중합체(C)는 방향족 비닐계 단량체 및 방향족 비닐계 단량체와 공중합 가능한 단량체를 공중합시켜 제조할 수 있다. 또한, 선택적으로 가공성 및 내열성을 부여하는 단량체를 더 공중합시켜 제조할 수 있다.The aromatic vinyl copolymer (C) may be prepared by copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer. It can also be prepared by further copolymerizing monomers which optionally provide processability and heat resistance.
방향족 비닐계 공중합체(C)는 방향족 비닐계 단량체 60 내지 90 중량% 및 방향족 비닐계 단량체와 공중합 가능한 단량체 10 내지 40 중량%를 중합시켜 제조할 수 있다.The aromatic vinyl copolymer (C) may be prepared by polymerizing 60 to 90% by weight of an aromatic vinyl monomer and 10 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer.
방향족 비닐계 단량체는 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, 파라 t-부틸스티렌, 에틸 스티렌, 비닐 크실렌, 모노클로로스티렌, 디클로로스티렌, 디브로모스티렌, 또는 이들의 혼합물일 수 있다. 바람직하게는 스티렌을 사용할 수 있다.The aromatic vinyl monomers are styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, or mixtures thereof Can be. Preferably styrene can be used.
방향족 비닐계 단량체와 공중합 가능한 단량체는 불포화 니트릴 단량체, 아크릴계 단량체, 또는 이들의 혼합물일 수 있다.The monomer copolymerizable with the aromatic vinyl monomer may be an unsaturated nitrile monomer, an acrylic monomer, or a mixture thereof.
불포화 니트릴계 단량체는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 또는 이들의 혼합물일 수 있다. 아크릴계 단량체는 메틸 아크릴레이트, 메틸 메타크릴레이트, 또는 이들의 혼합물일 수 있다.The unsaturated nitrile monomer may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or a mixture thereof. The acrylic monomers may be methyl acrylate, methyl methacrylate, or mixtures thereof.
방향족 비닐계 공중합체(C)는 내열성 및 가공성을 부여하기 위하여, 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체, 또는 이들의 혼합물을 0 내지 30 중량% 더 중합시킬 수 있다.The aromatic vinyl copolymer (C) may further polymerize 0 to 30% by weight of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, or a mixture thereof in order to impart heat resistance and processability.
불포화 카르복실산은 아크릴산 또는 메타크릴산일 수 있다. 불포화 카르복실산 무수물은 무수말레인산일 수 있다. 말레이미드계 단량체는 알킬, 또는 핵치환 말레이미드일 수 있다.The unsaturated carboxylic acid may be acrylic acid or methacrylic acid. The unsaturated carboxylic anhydride may be maleic anhydride. The maleimide monomer may be alkyl, or nuclear substituted maleimide.
본 발명에서, 방향족 비닐계 공중합체(C)는 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A), 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B), 방향족 비닐계 공중합체(C) 100 중량%에 대하여, 50 내지 80 중량% 포함될 수 있다. 방향족 비닐계 공중합체(C)의 함량이 80 중량% 초과인 경우, 열가소성 수지 조성물의 충격강도가 저하될 수 있다.In the present invention, the aromatic vinyl copolymer (C) is a rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure of a large particle size, and a rubber-modified aromatic vinyl graft copolymer having a core-shell structure of a small particle size. (B), 50 to 80% by weight based on 100% by weight of the aromatic vinyl copolymer (C). When the content of the aromatic vinyl copolymer (C) is more than 80% by weight, the impact strength of the thermoplastic resin composition may decrease.
(D) 탄소나노튜브(D) carbon nanotubes
본 발명에 따른 열가소성 수지 조성물은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 알려진 방법에 의해 제조되거나, 상업적으로 구입 가능한 탄소나노튜브(D)가 제한 없이 사용될 수 있다. 탄소나노튜브(D)는 열가소성 수지 조성물의 표면저항을 낮춰, 열가소성 수지 조성물의 전도성을 높이기 때문에, 프라이머 처리 없이도 정전도장을 가능하게 한다. The thermoplastic resin composition according to the present invention may be prepared by a method known to those skilled in the art, or commercially available carbon nanotubes (D) may be used without limitation. Since carbon nanotubes (D) lower the surface resistance of the thermoplastic resin composition and increase the conductivity of the thermoplastic resin composition, the carbon nanotube (D) enables electrostatic coating even without a primer treatment.
탄소나노튜브를 합성하는 방법은 전기방전법(Arc-discharge), 열분해법(pyrolysis), 레이저 증착법(Laser vaporization), 플라즈마 화학기상증착법(plasma chemical vapor deposition), 열화학 기상증착법(Thermal chemical vapor deposition), 전기분해법, flame 합성법 등이 있으나, 본 발명에서 사용된 탄소나노튜브(D)는 합성 방법에 관계없이 얻어진 탄소나노튜브 모두를 사용할 수 있다.The method of synthesizing carbon nanotubes is arc-discharge, pyrolysis, laser vaporization, plasma chemical vapor deposition, and thermal chemical vapor deposition. , Electrolysis, flame synthesis, and the like, but the carbon nanotubes (D) used in the present invention may use all of the obtained carbon nanotubes regardless of the synthesis method.
탄소나노튜브는 그 벽의 개수에 따라 단일벽탄소나노튜브(single wall carbon nanotube), 이중벽탄소타노튜브(double wall carbon nanotube), 다중벽탄소나노튜브(multi wall carbon nanotube), 절두된 원뿔형의 그래핀(truncated graphene)이 다수 적층된 내부가 비어 있는 중공관 형태를 가진 탄소나노섬유(cup-stacked carbon nanofiber)로 나눌 수 있다. 본 발명에서 사용되는 탄소나노튜브(D)는 그 종류에 제한을 두지 않으나, 다중벽탄소나노튜브를 사용하는 것이 경제적으로 바람직하다.Carbon nanotubes can be divided into single wall carbon nanotubes, double wall carbon nanotubes, multi wall carbon nanotubes, and truncated cones depending on the number of walls. It can be divided into a cup-stacked carbon nanofiber having a hollow tube shape in which a plurality of truncated graphenes are stacked. Carbon nanotubes (D) used in the present invention is not limited to the kind, it is economically preferable to use multi-walled carbon nanotubes.
탄소나노튜브(D)는 평균입경이 5 내지 100 nm이고, 평균길이가 1 내지 50 ㎛이며, 바람직하게는 평균입경이 5 내지 30 nm이고, 평균길이가 1 내지 50 ㎛일 수 있다.The carbon nanotubes (D) may have an average particle diameter of 5 to 100 nm, an average length of 1 to 50 μm, preferably an average particle diameter of 5 to 30 nm, and an average length of 1 to 50 μm.
본 발명에서, 탄소나노튜브(D)는 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A), 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B), 방향족 비닐계 공중합체(C) 100 중량부에 대하여, 1 내지 5 중량부로 포함될 수 있다. 탄소나노튜브(D)의 함량이 1 중량부 미만인 경우, 열가소성 수지 조성물의 전도성이 저하되고, 5 중량부 초과인 경우, 열가소성 수지 조성물의 충격강도가 저하될 수 있다.In the present invention, the carbon nanotube (D) is a rubber-modified aromatic vinyl graft copolymer (A) of a core-shell structure of a large particle size, a rubber-modified aromatic vinyl graft copolymer (B) of a core-shell structure of a small particle size (B) ), 1 to 5 parts by weight based on 100 parts by weight of the aromatic vinyl copolymer (C). When the content of the carbon nanotubes (D) is less than 1 part by weight, the conductivity of the thermoplastic resin composition is lowered, and when it is more than 5 parts by weight, the impact strength of the thermoplastic resin composition may be lowered.
(E) 도전제(E) conductive agent
열가소성 수지 조성물의 전도성을 향상시키기 위하여 도전제로 카본블랙을 더 사용할 수 있다. 상기 카본블랙은 우수한 전기전도성을 구현하기 위하여 비표면적이 50 내지 1500 ㎡/g이고, 평균입자크기가 10 내지 100 nm인 것이 바람직하다.In order to improve conductivity of the thermoplastic resin composition, carbon black may be further used as a conductive agent. The carbon black has a specific surface area of 50 to 1500 m 2 / g and an average particle size of 10 to 100 nm in order to implement excellent electrical conductivity.
카본블랙은 케첸블랙(ketjen black), 아세틸렌블랙(acetylene balck), 퍼니스블랙(furnace black), 채널블랙(channel balck), 팀칼카본블랙(timcal carbon black), 또는 이들의 혼합물일 수 있다. 이 중 전기전도성이 우수한 케첸블랙을 사용하는 것이 바람직하다.The carbon black may be ketjen black, acetylene balck, furnace black, channel black, timcal carbon black, or mixtures thereof. It is preferable to use Ketjen Black which is excellent in electrical conductivity among these.
카본블랙은 우수한 전기전도성을 가지나, 긁힘 또는 마찰에 의하여 카본입자가 탈락하기 쉬운 특성을 가지고 있어서, 마모량이 많이 발생한다는 문제점이 있다. 또한 카본블랙을 과량 사용하는 경우, 성형품의 압출성이 저하되는 문제점이 있다. 그러나 탄소나노튜브와 함께 적용하는 경우, 카본블랙의 함량을 현저하게 줄이면서도 일정 수준 이상의 전도성을 확보할 수 있다. 또한, 탄소나노튜브의 카본 피브릴 사이에 미세한 도전성 3차원 네트워크 구조를 형성할 수 있어, 표면 저항값의 안정화와 카본입자 탈락의 안정화를 이룰 수 있다. Carbon black has excellent electrical conductivity, but has a property that carbon particles are likely to fall off due to scratches or friction, and thus, a large amount of wear occurs. In addition, when an excessive amount of carbon black is used, there is a problem that the extrudability of the molded article is reduced. However, when applied with carbon nanotubes, it is possible to secure a certain level of conductivity while significantly reducing the content of carbon black. Further, a fine conductive three-dimensional network structure can be formed between the carbon fibrils of the carbon nanotubes, thereby achieving stabilization of the surface resistance value and stabilization of carbon particle dropping.
본 발명에서, 도전제(E)는 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A), 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B), 방향족 비닐계 공중합체(C) 100 중량부에 대하여, 0.5 내지 10 중량부 포함될 수 있다. 도전제(E)의 함량이 0.5 중량부 미만인 경우, 전기전도성이 저하되고, 10 중량부 초과인 경우, 기계적 물성 및 압출성이 저하될 수 있다.In the present invention, the conductive agent (E) is a rubber-modified aromatic vinyl graft copolymer (A) having a core-shell structure of a large particle size, and a rubber-modified aromatic vinyl graft copolymer (B) having a core-shell structure of a small particle size. , Based on 100 parts by weight of the aromatic vinyl copolymer (C), 0.5 to 10 parts by weight may be included. When the content of the conductive agent (E) is less than 0.5 parts by weight, the electrical conductivity is lowered, and when it is more than 10 parts by weight, mechanical properties and extrudability may be lowered.
(F) 첨가제(F) additive
본 발명의 열가소성 수지 조성물은 수지 조성물 각각의 용도에 따라 첨가제(F)를 더 포함할 수 있다.The thermoplastic resin composition of the present invention may further include an additive (F) according to each use of the resin composition.
열가소성 수지 조성물은 충격보강재, 적하 방지제, 산화방지제, 가소제, 열안정제, 광안정제, 상용화제, 내후안정제, 안료, 염료, 착색제, 무기물 첨가제, 또는 이들의 혼합물을 더 포함할 수 있다.The thermoplastic resin composition may further include an impact modifier, an antidropping agent, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weather stabilizer, a pigment, a dye, a colorant, an inorganic additive, or a mixture thereof.
본 발명에서, 첨가제(F)는 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A), 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B), 방향족 비닐계 공중합체(C) 100 중량부에 대하여, 10 중량부 이하, 바람직하게는 0.0001 중량부 내지 10 중량부 이하로 포함될 수 있다.In the present invention, the additive (F) is a rubber-modified aromatic vinyl graft copolymer (A) of a core-shell structure of a large particle size, a rubber-modified aromatic vinyl graft copolymer (B) of a core-shell structure of a small particle size, 10 parts by weight or less, preferably 0.0001 parts by weight to 10 parts by weight or less based on 100 parts by weight of the aromatic vinyl copolymer (C).
본 발명에 따른 열가소성 수지 조성물은 수지 조성물을 제조하는 공지의 방법에 의해서 제조될 수 있다. 예를 들어, 본 발명에 따른 열가소성 수지 조성물은 본 발명의 구성 성분과 기타 첨가제들을 동시에 혼합한 후 압출기 내에서 용융 압출하는 방법에 의하여 펠렛의 형태로 제조될 수 있다.The thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition. For example, the thermoplastic resin composition according to the present invention may be prepared in the form of pellets by a method of simultaneously mixing the components of the present invention and other additives and then melt extrusion in an extruder.
본 발명에 따른 열가소성 수지 조성물을 성형하여 성형품을 제조하는 방법에는 특별한 제한이 없다. 예를 들어, 압출, 사출 혹은 캐스팅 성형 방법 등이 적용될 수 있다. 성형방법은 본 발명이 속하는 분야에서 통상의 지식을 가진 자에 의해 용이하게 실시될 수 있다.There is no particular limitation on the method for producing a molded article by molding the thermoplastic resin composition according to the present invention. For example, an extrusion, injection or cast molding method may be applied. Molding method can be easily carried out by those skilled in the art.
본 발명의 성형품은 ASTM D256에 준하여 23 ℃에서 측정한 1/8" 두께의 성형품의 Izod 충격강도가 15 내지 40 kgf·cm/cm이다.The molded article of the present invention has an Izod impact strength of 15 to 40 kgf · cm / cm for a molded article of 1/8 ″ thickness measured at 23 ° C. in accordance with ASTM D256.
본 발명의 성형품은 ASTM D257에 준하여 Wolfgang Warmbler社의 SRM-100을 사용하여 측정한 표면저항이 10-1 내지 1011 Ω/□이다.The molded article of the present invention has a surface resistance of 10 −1 to 10 11 μs / □ measured using Wolfgang Warmbler's SRM-100 according to ASTM D257.
본 발명의 성형품은 ASTM D257에 준하여 YOKOGAWA社의 MY40을 사용하여 측정한 체적저항(Ω·cm)이 10-1 내지 108 Ω·cm이다.The molded article of the present invention has a volume resistivity (Ω · cm) of 10 −1 to 10 8 Ω · cm measured using MY40 manufactured by YOKOGAWA Co., Ltd. in accordance with ASTM D257.
본 발명은 하기의 실시예에 의해 보다 구체화될 것이나, 하기의 실시예는 본 발명을 예시하기 위한 목적으로 사용될 뿐이며 본 발명의 보호범위를 한정하고자 하는 것은 아니다.The present invention will be further illustrated by the following examples, which are used only for the purpose of illustrating the invention and are not intended to limit the scope of the invention.
실시예Example
실시예 및 비교실시예에서 사용된 각 구성성분은 다음과 같다.Each component used in the Example and the comparative example is as follows.
(A) 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A) Rubber-modified aromatic vinyl graft copolymer of core-shell structure of large particle size
평균입경이 2,570 Å인 g-ABS로 제일모직社의 AB03-CHA를 사용하였다.Cheil Industries AB03-CHA was used as g-ABS with an average particle diameter of 2,570 mm3.
(B) 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B) Rubber-modified aromatic vinyl graft copolymer of core-shell structure of small particle size
평균입경이 1,300 Å인 g-ABS로 제일모직社의 AB03-CHT를 사용하였다.Cheil Industries AB03-CHT was used as g-ABS with an average particle diameter of 1,300 mm 3.
(C) 방향족 비닐계 공중합체(C) aromatic vinyl copolymer
(C1) 중량평균분자량이 95,000 g/mol인 SAN으로 제일모직社의 CA03-AP-70을 사용하였다.(C1) Cheil Industries' CA03-AP-70 was used as a SAN having a weight average molecular weight of 95,000 g / mol.
(C2) 중량평균분자량이 125,000 g/mol인 SAN으로 제일모직社의 CA03-AP-30을 사용하였다.(C2) Cheil Industries' CA03-AP-30 was used as a SAN having a weight average molecular weight of 125,000 g / mol.
(D) 탄소나노튜브(D) carbon nanotubes
평균입경이 5 내지 30 nm이고, 평균길이가 1 내지 50 ㎛인 탄소나노튜브로 ShowaDenko社의 다중벽 탄소나노튜브인 VGCF-X를 사용하였다. As a carbon nanotube having an average particle diameter of 5 to 30 nm and an average length of 1 to 50 μm, VGCF-X, a multi-walled carbon nanotube manufactured by ShowaDenko, was used.
실시예 1 및 비교실시예 1 내지 5Example 1 and Comparative Examples 1 to 5
상기 각 구성성분을 하기 표 1 및 2에 기재된 함량대로 건식 혼합한 뒤, 이 혼합물을 L/D=35, Φ=45 mm인 이축 압출기를 사용하여 230 내지 260 ℃에서 압출하였으며, 이 압출물을 펠렛 형태로 제조하였다. 펠렛 형태의 압출물을 80 ℃에서 4시간 건조 한 후 10 oz 사출기에서 사출온도 230 내지 260 ℃ 하에서 사출하여 각종 물성을 측정하기 위한 시편을 제조하였다. After dry mixing each of the components according to the contents shown in Tables 1 and 2, the mixture was extruded at 230 to 260 ° C. using a twin screw extruder having L / D = 35 and Φ = 45 mm. Prepared in pellet form. The pellet-form extrudates were dried at 80 ° C. for 4 hours and then injected at a injection temperature of 230 to 260 ° C. in a 10 oz injection machine to prepare specimens for measuring various physical properties.
하기 표에서 (A), (B) 및 (C)의 혼합비는 (A), (B) 및 (C) 전체 100 중량%에 대하여 중량%로 나타낸 것이고, (D)는 (A), (B) 및 (C) 전체 100 중량부에 대하여 중랑부로 나타낸 것이다.In the following table, the mixing ratios of (A), (B) and (C) are represented by weight percent with respect to 100% by weight of (A), (B) and (C), and (D) is (A), (B) ) And (C) it is shown as a middle part with respect to 100 weight part of total.
표 1
Figure PCTKR2013007805-appb-T000001
 Table 1
Figure PCTKR2013007805-appb-T000001
제조된 시편에 대하여 하기와 같은 방법으로 물성을 측정하였으며 그 결과를 표 2 및 3에 나타내었다.The physical properties of the prepared specimens were measured by the following method, and the results are shown in Tables 2 and 3.
(1) Izod 충격강도(kgf·cm/cm): ASTM D 256에 준하여 23 ℃에서 1/8" 두께에서 측정하였다.(1) Izod impact strength (kgfcm / cm): measured in 1/8 "thickness at 23 ℃ according to ASTM D 256.
(2) 표면저항(Ω/□): ASTM D257에 준하여 Wolfgang Warmbler社의 SRM-100을 사용하여 측정하였다.(2) Surface resistance (Ω / □): measured using Wolfgang Warmbler's SRM-100 according to ASTM D257.
(3) 체적저항(Ω·cm): ASTM D257에 준하여 YOKOGAWA社의 MY40을 사용하여 측정하였다.(3) Volume resistivity (Ωcm): It measured using MY40 by YOKOGAWA company based on ASTMD257.
(4) 도장효율(%): 두께 2 mm의 A4 크기의 시편을 사출하여, 시편에 40 KV의 전압을 걸어주어 도장을 하고 건조를 한 후, 도장 전·후의 무게를 비교하였다.(4) Coating efficiency (%): A4 size specimens with a thickness of 2 mm were injected, applied with a voltage of 40 KV to the specimens, painted and dried, and the weights before and after coating were compared.
표 2
Figure PCTKR2013007805-appb-T000002
 TABLE 2
Figure PCTKR2013007805-appb-T000002
표 3
Figure PCTKR2013007805-appb-T000003
 TABLE 3
Figure PCTKR2013007805-appb-T000003
상기 표 2에 나타나 있듯이, 본원발명의 범위에 포함되는 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A), 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B), 방향족 비닐계 공중합체(C) 및 탄소나노튜브(D)를 사용한 실시예 1은 탄소나노튜브(D) 사용에 따라 표면저항이 저하되어 전도성이 향상되었다. 또한, 대입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)와 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)를 함께 사용하고 특정범위의 중량평균분자량을 갖는 방향족 비닐계 공중합체(C)를 사용하여, 탄소나노튜브(D) 사용에 따른 충격강도 저하를 방지하였다.As shown in Table 2, the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure of the large particle size and the rubber-modified aromatic vinyl graft air of the core-shell structure of the small particle diameter included in the scope of the present invention In Example 1 using the copolymer (B), the aromatic vinyl copolymer (C) and the carbon nanotubes (D), the surface resistance was reduced according to the use of the carbon nanotubes (D), thereby improving the conductivity. In addition, a rubber-modified aromatic vinyl graft copolymer (A) having a large particle size core-shell structure and a rubber-modified aromatic vinyl graft copolymer (B) having a small particle size core-shell structure are used together and have a specific range of weight. An aromatic vinyl copolymer (C) having an average molecular weight was used to prevent a decrease in impact strength due to the use of carbon nanotubes (D).
반면, 탄소나노튜브(D)를 사용하지 않은 비교실시예 1은 표면저항이 너무 높아 측정할 수 없었으며, 중량평균분자량이 큰 방향족 비닐계 공중합체(C)를 사용한 비교실시예 2는 전도성 및 충격강도가 모두 저하되었다. 또한, 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)를 본원발명의 함량범위를 벗어나 사용한 비교실시예 3 및 소입경의 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)를 사용하지 않은 비교실시예 4는 충격강도가 저하되었다. 방향족 비닐계 공중합체(C)의 중량평균분자량의 범위를 벗어나 사용한 비교실시예 5는 전도성 및 충격강도가 모두 저하되었다. On the other hand, Comparative Example 1 without using carbon nanotubes (D) was too high surface resistance could not be measured, Comparative Example 2 using an aromatic vinyl copolymer (C) having a large weight average molecular weight is conductive and Both impact strengths were reduced. In addition, Comparative Example 3 using a rubber-modified aromatic vinyl-based graft copolymer (B) having a small particle size core-shell structure, and a rubber-modified aromatic vinyl-based graphene having a core-shell structure having a small particle size, out of the content range of the present invention. In Comparative Example 4 without using the copolymer (B), the impact strength was lowered. In Comparative Example 5 used out of the range of the weight average molecular weight of the aromatic vinyl copolymer (C), both the conductivity and the impact strength were reduced.
상기 표 3에서 알 수 있듯이, 본원발명의 범위에 포함되는 실시예 1은 본원발명의 범위에 포함되지 않은 비교실시예 1 및 2에 비해 체적저항 및 도장효율이 우수하였다.As can be seen in Table 3, Example 1 included in the scope of the present invention was superior in volume resistance and coating efficiency compared to Comparative Examples 1 and 2 not included in the scope of the present invention.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (17)

  1. (A) 평균입경이 2,000 내지 5,000 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체 15 내지 35 중량%; (A) 15 to 35% by weight of a rubber-modified aromatic vinyl graft copolymer having a core-shell structure having an average particle diameter of 2,000 to 5,000 mm 3;
    (B) 평균입경이 500 내지 1,500 Å인 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체 5 내지 15 중량%; 및(B) 5 to 15% by weight of a rubber-modified aromatic vinyl graft copolymer having a core-shell structure having an average particle diameter of 500 to 1,500 mm 3; And
    (C) 중량평균분자량이 70,000 내지 120,000 g/mol인 방향족 비닐계 공중합체 50 내지 80 중량%;(C) 50 to 80% by weight of an aromatic vinyl copolymer having a weight average molecular weight of 70,000 to 120,000 g / mol;
    를 포함하는 기초수지 100 중량부에 대하여,Based on 100 parts by weight of the base resin including:
    (D) 탄소나노튜브 1 내지 5 중량부;(D) 1 to 5 parts by weight of carbon nanotubes;
    를 포함하는 전도성 열가소성 수지 조성물.Conductive thermoplastic resin composition comprising a.
  2. 제1항에 있어서, 상기 탄소나노튜브(D)는 평균입경이 5 내지 100 nm이고, 평균길이가 1 내지 50 ㎛인 것을 특징으로 하는 전도성 열가소성 수지 조성물.The conductive thermoplastic resin composition according to claim 1, wherein the carbon nanotubes (D) have an average particle diameter of 5 to 100 nm and an average length of 1 to 50 µm.
  3. 제1항에 있어서, 상기 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(A)는 평균입경이 50 내지 500 Å인 고무질 중합체 5 내지 65 중량%에, 방향족 비닐계 단량체 34 내지 94 중량% 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체 1 내지 30 중량%를 그라프트 중합시킨 것이고, 상기 코어-쉘 구조의 고무변성 방향족 비닐계 그라프트 공중합체(B)는 평균입경이 20 내지 300 Å인 고무질 중합체 5 내지 65 중량%에, 방향족 비닐계 단량체 34 내지 94 중량% 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체 1 내지 30 중량%를 그라프트 중합시킨 것임을 특징으로 하는 전도성 열가소성 수지 조성물.According to claim 1, wherein the rubber-modified aromatic vinyl graft copolymer (A) of the core-shell structure is 34 to 94 weight of the aromatic vinyl monomer in 5 to 65% by weight of the rubbery polymer having an average particle diameter of 50 to 500 mm 3 % And 1 to 30% by weight of a monomer copolymerizable with the aromatic vinyl monomer are graft polymerized, and the rubber-modified aromatic vinyl graft copolymer (B) having the core-shell structure has an average particle diameter of 20 to 300 mm 3. A conductive thermoplastic resin composition comprising graft polymerization of 34 to 94% by weight of an aromatic vinyl monomer and 1 to 30% by weight of a monomer copolymerizable with the aromatic vinyl monomer to 5 to 65% by weight of a rubbery polymer.
  4. 제3항에 있어서, 상기 고무질 중합체는 디엔계 고무, 디엔계 고무에 수소를 첨가한 포화고무, 아크릴레이트계 고무, 에틸렌-프로필렌-디엔 단량체 삼원공중합체, 실리콘계 고무 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 전도성 열가소성 수지 조성물.4. The rubbery polymer according to claim 3, wherein the rubbery polymer is selected from the group consisting of diene rubber, saturated rubber having hydrogenated diene rubber, acrylate rubber, ethylene-propylene-diene monomer terpolymer, silicone rubber and mixtures thereof. A conductive thermoplastic resin composition, characterized in that selected.
  5. 제3항에 있어서, 상기 방향족 비닐계 단량체는 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, 파라 t-부틸스티렌, 에틸스티렌, 비닐 크실렌, 모노클로로스티렌, 디클로로스티렌, 디브로모스티렌, 비닐 나프탈렌 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 전도성 열가소성 수지 조성물.The method of claim 3, wherein the aromatic vinyl monomer is styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t- butyl styrene, ethyl styrene, vinyl xylene, monochloro styrene, dichloro styrene, dibro A conductive thermoplastic resin composition, characterized in that it is selected from the group consisting of mostyrene, vinyl naphthalene and mixtures thereof.
  6. 제3항에 있어서, 상기 방향족 비닐계 단량체와 공중합이 가능한 단량체는 불포화 니트릴계 단량체, 아크릴계 단량체 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 전도성 열가소성 수지 조성물.The conductive thermoplastic resin composition of claim 3, wherein the monomer copolymerizable with the aromatic vinyl monomer is selected from the group consisting of unsaturated nitrile monomers, acrylic monomers, and mixtures thereof.
  7. 제3항에 있어서, 상기 고무질 중합체에 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체 및 이들의 혼합물로 이루어진 군으로부터 선택되는 단량체가 0 내지 15 중량%로 더 그라프트 중합되어 있는 것을 특징으로 하는 전도성 열가소성 수지 조성물.According to claim 3, wherein the rubber polymer is selected from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic anhydride, maleimide monomers and mixtures thereof is further graft polymerized to 0 to 15% by weight. A conductive thermoplastic resin composition.
  8. 제1항에 있어서, 상기 방향족 비닐계 공중합체(C)는 방향족 비닐계 단량체 60 내지 90 중량% 및 방향족 비닐계 단량체와 공중합 가능한 단량체 10 내지 40 중량%를 중합시킨 것임을 특징으로 하는 전도성 열가소성 수지 조성물.According to claim 1, wherein the aromatic vinyl copolymer (C) is a conductive thermoplastic resin composition characterized in that the polymerization of 60 to 90% by weight of the aromatic vinyl monomer and 10 to 40% by weight of the monomer copolymerizable with the aromatic vinyl monomer. .
  9. 제8항에 있어서, 상기 방향족 비닐계 단량체는 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, 파라 t-부틸스티렌, 에틸스티렌, 비닐 크실렌, 모노클로로스티렌, 디크롤로스티렌, 디브로모스티렌 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 전도성 열가소성 수지 조성물.The method of claim 8, wherein the aromatic vinyl monomer is styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t- butyl styrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, di A conductive thermoplastic resin composition, characterized in that selected from the group consisting of bromostyrene and mixtures thereof.
  10. 제8항에 있어서, 상기 방향족 비닐계 단량체와 공중합 가능한 단량체는 불포화 니트릴계 단량체, 아크릴계 단량체 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 전도성 열가소성 수지 조성물.The conductive thermoplastic resin composition of claim 8, wherein the monomer copolymerizable with the aromatic vinyl monomer is selected from the group consisting of unsaturated nitrile monomers, acrylic monomers, and mixtures thereof.
  11. 제8항에 있어서, 상기 방향족 비닐계 공중합체(C)에 불포화 카르복실산, 불포화 카르복실산 무수물, 말레이미드계 단량체 및 이들의 혼합물로 이루어진 군으로부터 선택되는 단량체가 0 내지 30 중량% 더 중합되어 있는 것을 특징으로 하는 전도성 열가소성 수지 조성물.The monomer according to claim 8, further comprising 0 to 30% by weight of a monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimide monomers and mixtures thereof in the aromatic vinyl copolymer (C). A conductive thermoplastic resin composition, characterized in that.
  12. 제1항에 있어서, 카본블랙을 더 포함하는 것을 특징으로 하는 전도성 열가소성 수지 조성물.The conductive thermoplastic resin composition of claim 1, further comprising carbon black.
  13. 제1항에 있어서, 충격보강재, 적하 방지제, 산화 방지제, 가소제, 열안정제, 광안정제, 상용화제, 내후안정제, 안료, 염료, 착색제, 무기물 첨가제 및 이들의 혼합물로 이루어진 군으로부터 선택되는 첨가제를 더 포함하는 것을 특징으로 하는 전도성 열가소성 수지 조성물.The additive of claim 1 further comprising an impact modifier, an antidropping agent, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weather stabilizer, a pigment, a dye, a colorant, an inorganic additive, and a mixture thereof. A conductive thermoplastic resin composition, comprising:
  14. 제1항 내지 제13항 중 어느 한 항에 따른 전도성 열가소성 수지 조성물로 성형된 성형품.A molded article molded from the conductive thermoplastic resin composition according to any one of claims 1 to 13.
  15. 제14항에 있어서, ASTM D256에 준하여 23 ℃에서 측정한 1/8" 두께의 성형품의 Izod 충격강도가 20 내지 30 kgf·cm/cm인 것을 특징으로 하는 성형품.15. The molded article according to claim 14, wherein the Izod impact strength of the molded article having a thickness of 1/8 "measured at 23 DEG C according to ASTM D256 is 20 to 30 kgfcm / cm.
  16. 제14항에 있어서, ASTM D257에 준하여 Wolfgang Warmbler社의 SRM-100을 사용하여 측정한 표면저항이 10-1 내지 1011 Ω/□인 것을 특징으로 하는 성형품.The molded article according to claim 14, wherein the surface resistance measured using Wolfgang Warmbler's SRM-100 in accordance with ASTM D257 is 10 -1 to 10 11 kPa / square.
  17. 제14항에 있어서, ASTM D257에 준하여 YOKOGAWA社의 MY40을 사용하여 측정한 체적저항이 10-1 내지 108 Ω·cm인 것을 특징으로 하는 성형품.The molded article according to claim 14, wherein the volume resistance measured by using MY40 manufactured by YOKOGAWA Co., Ltd. is 10 -1 to 10 8 Pa · cm in accordance with ASTM D257.
PCT/KR2013/007805 2013-05-31 2013-08-30 Thermoplastic resin composition having excellent conductivity and impact strength WO2014193039A1 (en)

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